EP0668372A1 - Film de diamant semi-transparent - Google Patents

Film de diamant semi-transparent Download PDF

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Publication number
EP0668372A1
EP0668372A1 EP95300516A EP95300516A EP0668372A1 EP 0668372 A1 EP0668372 A1 EP 0668372A1 EP 95300516 A EP95300516 A EP 95300516A EP 95300516 A EP95300516 A EP 95300516A EP 0668372 A1 EP0668372 A1 EP 0668372A1
Authority
EP
European Patent Office
Prior art keywords
carbon
mixture
hydrogen
diamond
diamond film
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP95300516A
Other languages
German (de)
English (en)
Inventor
Thomas Richard Anthony
James Fulton Fleischer
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
General Electric Co
Original Assignee
General Electric Co
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by General Electric Co filed Critical General Electric Co
Publication of EP0668372A1 publication Critical patent/EP0668372A1/fr
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/278—Diamond only doping or introduction of a secondary phase in the diamond
    • C—CHEMISTRY; METALLURGY
    • C30—CRYSTAL GROWTH
    • C30B—SINGLE-CRYSTAL GROWTH; UNIDIRECTIONAL SOLIDIFICATION OF EUTECTIC MATERIAL OR UNIDIRECTIONAL DEMIXING OF EUTECTOID MATERIAL; REFINING BY ZONE-MELTING OF MATERIAL; PRODUCTION OF A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; SINGLE CRYSTALS OR HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; AFTER-TREATMENT OF SINGLE CRYSTALS OR A HOMOGENEOUS POLYCRYSTALLINE MATERIAL WITH DEFINED STRUCTURE; APPARATUS THEREFOR
    • C30B29/00—Single crystals or homogeneous polycrystalline material with defined structure characterised by the material or by their shape
    • C30B29/02—Elements
    • C30B29/04—Diamond
    • C—CHEMISTRY; METALLURGY
    • C23—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; CHEMICAL SURFACE TREATMENT; DIFFUSION TREATMENT OF METALLIC MATERIAL; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL; INHIBITING CORROSION OF METALLIC MATERIAL OR INCRUSTATION IN GENERAL
    • C23C—COATING METALLIC MATERIAL; COATING MATERIAL WITH METALLIC MATERIAL; SURFACE TREATMENT OF METALLIC MATERIAL BY DIFFUSION INTO THE SURFACE, BY CHEMICAL CONVERSION OR SUBSTITUTION; COATING BY VACUUM EVAPORATION, BY SPUTTERING, BY ION IMPLANTATION OR BY CHEMICAL VAPOUR DEPOSITION, IN GENERAL
    • C23C16/00—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes
    • C23C16/22—Chemical coating by decomposition of gaseous compounds, without leaving reaction products of surface material in the coating, i.e. chemical vapour deposition [CVD] processes characterised by the deposition of inorganic material, other than metallic material
    • C23C16/26—Deposition of carbon only
    • C23C16/27—Diamond only
    • C23C16/271—Diamond only using hot filaments

Definitions

  • the present invention relates to a chemical vapor deposition (CVD) method for making semi-transparent free-standing polycrystalline diamond film. More particularly, the present invention relates to the formation of diamond film using a mixture comprised of hydrogen and a carbon polyfluoride, such as carbon tetrafluoride, in a heated reaction zone adjacent to a substrate, such as molybdenum.
  • CVD chemical vapor deposition
  • continuous free-standing substantially transparent diamond film can be made by utilizing a mixture of hydrogen and methane in a heated reaction zone. It has been found that diamond films made from hydrogenmethane mixtures can have various degrees of transparency depending upon such factors as film thickness, the volume % of the methane used in the reaction mixture during film formation etc. As discussed in U.S. 5,110,579, disassociation of hydrogen atoms and methane in a heated reaction zone is sufficient to generate active carbon-hydrogen species leading to diamond film formation.
  • Copending application RD-23105 shows that diamond films having improved transparency can be made by the chemical vapor deposition (CVD) of mixtures of hydrogen and a carbon polychloride as compared to CVD films made from hydrogen and methane. It would be desirable to provide additional procedures for making free-standing semi-transparent diamond films.
  • CVD chemical vapor deposition
  • the present invention is based on the discovery that free-standing, substantially transparent, semi-transparent, or translucent polycrystalline diamond film, having a thickness of at least 50 microns, such as up to 5000 microns, and preferably 200 to 1000 microns, can be made by using a mixture of hydrogen and a carbon-fluorine containing material, such as carbon tetrafluoride, in a heated reaction zone. It has been found that such diamond film has an improved degree of "optical transparency" and thermal conductivity. Optical transparency is an empirical definition used to establish the degree of transparency of diamond film made in accordance with the practice of the invention. The optical transparency of an unevaluated diamond film is determined by comparing it with a standard transparent diamond film having a comparable thickness.
  • a standard diamond film is a diamond film made in accordance with the procedure shown by Anthony et al, U.S. patent 5,110,579.
  • the sample diamond film having approximately the same thickness as the standard is placed side by side under a visible light source with the standard diamond film on printed text, such as a U.S. patent.
  • the degree of optical transparency can be determined empirically by reading the printed text through the diamonds.
  • the fluorine containing diamond films made in accordance with the practice of the invention also have been found to have enhanced thermal conductivity as compared to CVD diamond made by using a mixture of hydrogen with either methane or a carbon-polychloride which is made in accordance with copending application RD-23105.
  • a continuous free-standing polycrystalline diamond film having a thickness of at least 50 microns comprising (A) substantially vertical columnar diamond crystals having a ⁇ 110> orientation perpendicular to the base and up to 10,000 parts per million of chemically combined fluorine atoms, or a mixture of fluorine atoms and hydrogen atoms which are sufficient to substantially saturate dangling carbon atoms at diamond crystal grain boundaries, carbon dislocations, and carbon valance vacancies and (B) diamond crystal grain boundaries separating the columnar diamond crystals of (A), where the diamond crystal grain boundaries have a 70°-90° orientation to the diamond crystal base.
  • a method of making a non- adherent free-standing, semi-transparent polycrystalline diamond film on a substrate comprises, passing a mixture of hydrogen and a carbon-fluorine containing material through a heated reaction zone at a temperature of about 700°C to about 900°C and at a pressure from about 3 to about 24 torr which is sufficient to generate active atomic species comprising carbon-F species, or a mixture of carbon-F species and carbon-hydrogen species in the heated reaction zone maintained at a distance of from about 0.3 to about 1 centimeter from the surface of the substrate, where the mixture of hydrogen and the carbon-fluorine containing material introduced into the heated reaction zone is a member selected from the group consisting of,
  • FIG. 1 A typical apparatus which can be used to form the transparent polycrystalline diamond film of the present invention is shown by the drawing.
  • the drawing shows a quartz bell jar having a metal flange which rests on a base. Inside the quartz bell jar, there is shown a support structure for a filament and several adjacent substrate sections.
  • a quartz bell jar at 10 which be 20''-30'' tall and about 4''-6'' wide having a metal collar at its base at 11 and a gas inlet at the top at 12 .
  • the metal collar portion rests on a rubber seal at 13 which can be Neoprene rubber.
  • the rubber seal is supported by a metal base, such as steel base structure at 14 which has a vacuum opening at 15 .
  • the filament is secured by a screw at 21 to a metal plug at 22 which passes through a quartz insulating collar at 23 which is supported by an extension at 24 .
  • Electrical contacts are shown from the plug at 25 to a stud at 26 which is insulated from the metal base at 27 .
  • polycrystalline diamond films made in accordance with the practice of the present invention can be used in a variety of glazing applications as well as heat sinks or semiconductors.
  • a mixture of about 1 volume % methane, about 0.5 volume % carbon tetrafluoride, and about 98.5 volume % hydrogen measured under atmospheric conditions was introduced into a reaction vessel as shown by in the drawing.
  • a gas flow rate of about 400 cubic centimeters per minute was maintained.
  • the tungsten filament was maintained at a temperature between about 2000°C to 2100°C
  • a separation of about 10 millimeters was maintained between the filament and the molybdenum substrate during the deposition which lasted about 34 days.
  • the substrate temperature was estimated at about 734°C during the deposition period.
  • fluorinated diamond film 1 having a thickness of about 255 microns separated from the substrate during the cooling period.
  • fluorinated diamond film 2 a transparent diamond film having a thickness substantially similar to fluorinated diamond film 1 and referred to hereinafter as "fluorinated diamond film 2".
  • a transparent diamond film is prepared in accordance with the method of Anthony et al, U.S. 5,110,579.
  • a reaction mixture is used consisting of about 1.5 volume % of methane and 98.5 volume % of hydrogen.
  • the standard having a thickness substantially similar in microns to fluorinated diamond films 1 and 2.
  • the optical transparencies of the fluorinated diamond films 1 and 2 were found to be substantially greater than the standard diamond film with respect to the clarity of printed text read through the diamonds when placed side by side under a fluorescent light.
  • fluorinated diamonds 1 and 2 were found to have enhanced thermal conductivity over the standard when measured by the Mirage technique shown by R. W. Pryor et al proceedings of the Second International Conference On New Diamond Science And Technology, p. 863(1990).

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  • Chemical & Material Sciences (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Metallurgy (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Inorganic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Crystals, And After-Treatments Of Crystals (AREA)
  • Carbon And Carbon Compounds (AREA)
  • Chemical Vapour Deposition (AREA)
EP95300516A 1994-02-16 1995-01-27 Film de diamant semi-transparent Withdrawn EP0668372A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US19567394A 1994-02-16 1994-02-16
US195673 1994-02-16

Publications (1)

Publication Number Publication Date
EP0668372A1 true EP0668372A1 (fr) 1995-08-23

Family

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Family Applications (1)

Application Number Title Priority Date Filing Date
EP95300516A Withdrawn EP0668372A1 (fr) 1994-02-16 1995-01-27 Film de diamant semi-transparent

Country Status (3)

Country Link
EP (1) EP0668372A1 (fr)
JP (1) JPH07309697A (fr)
KR (1) KR950032731A (fr)

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001589A1 (fr) * 1997-07-01 1999-01-14 E.I. Du Pont De Nemours And Company Revetements en carbone semblable a du diamant non colore
WO2000079020A1 (fr) * 1999-06-18 2000-12-28 Nissin Electric Co., Ltd. Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4843785B2 (ja) * 2006-02-28 2011-12-21 国立大学法人東北大学 気相ダイヤモンド膜のコーティング方法及び装置
JP4714208B2 (ja) * 2007-11-22 2011-06-29 キヤノンアネルバ株式会社 発熱体ｃｖｄ装置及び成膜方法

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0417512A1 (fr) * 1989-09-14 1991-03-20 General Electric Company Films de diamant transparents et méthode pour leur fabrication
EP0487292A1 (fr) * 1990-11-22 1992-05-27 Sumitomo Electric Industries, Limited Outil en diamant polycrystallin et méthode pour sa production
US5238705A (en) * 1987-02-24 1993-08-24 Semiconductor Energy Laboratory Co., Ltd. Carbonaceous protective films and method of depositing the same

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5238705A (en) * 1987-02-24 1993-08-24 Semiconductor Energy Laboratory Co., Ltd. Carbonaceous protective films and method of depositing the same
EP0417512A1 (fr) * 1989-09-14 1991-03-20 General Electric Company Films de diamant transparents et méthode pour leur fabrication
EP0487292A1 (fr) * 1990-11-22 1992-05-27 Sumitomo Electric Industries, Limited Outil en diamant polycrystallin et méthode pour sa production

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
BAGLIO J A ET AL: "Studies of stress related issues in microwave CVD diamond on (100) silicon substrates", APPLIED DIAMOND CONFERENCE, AUBURN, AL, USA, 17-22 AUG. 1991, vol. 212, no. 1-2, ISSN 0040-6090, THIN SOLID FILMS, 15 MAY 1992, SWITZERLAND, pages 180 - 185, XP025730619, DOI: doi:10.1016/0040-6090(92)90518-G *
GRAHAM R J ET AL: "Cathodoluminescence from diamond films grown by plasma-enhanced chemical vapor deposition in dilute CO/H/sub 2/, CF/sub 4//H/sub 2/, and CH/sub 4//H/sub 2/ mixtures", APPLIED PHYSICS LETTERS, 4 NOV. 1991, USA, vol. 59, no. 19, ISSN 0003-6951, pages 2463 - 2465 *

Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1999001589A1 (fr) * 1997-07-01 1999-01-14 E.I. Du Pont De Nemours And Company Revetements en carbone semblable a du diamant non colore
WO2000079020A1 (fr) * 1999-06-18 2000-12-28 Nissin Electric Co., Ltd. Film de carbone, procede de formation associe, article recouvert de ce film, et procede de preparation de cet article
US6652969B1 (en) 1999-06-18 2003-11-25 Nissin Electric Co., Ltd Carbon film method for formation thereof and article covered with carbon film and method for preparation thereof

Also Published As

Publication number Publication date
JPH07309697A (ja) 1995-11-28
KR950032731A (ko) 1995-12-22

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